WO2012086606A1 - Oil-repellent waterproof air-permeable filter and method for producing same - Google Patents
Oil-repellent waterproof air-permeable filter and method for producing same Download PDFInfo
- Publication number
- WO2012086606A1 WO2012086606A1 PCT/JP2011/079415 JP2011079415W WO2012086606A1 WO 2012086606 A1 WO2012086606 A1 WO 2012086606A1 JP 2011079415 W JP2011079415 W JP 2011079415W WO 2012086606 A1 WO2012086606 A1 WO 2012086606A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- fluoropolymer
- monomer
- mass
- repellent
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0421—Rendering the filter material hydrophilic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0478—Surface coating material on a layer of the filter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
Definitions
- the present invention relates to an oil-repellent waterproof breathable filter and a method for producing the same.
- a waterproof coating of a PTFE resin is applied to a hydrophobic porous membrane such as a porous polytetrafluoroethylene (hereinafter referred to as “PTFE”) resin sheet or a porous polyolefin resin sheet, a nonwoven fabric, a mesh or the like.
- PTFE porous polytetrafluoroethylene
- the applied one can be used as a waterproof breathable membrane (breathable filter).
- waterproof breathable filters for electrical components mounted on automobiles adhere to the oil vapors of various automobile oils such as engine oil, torque converter oil, power steering oil, etc. in the engine room, or remove organic solvents used under the chassis. It is conceivable that the contained rust preventive agent or the like, or the detergent for automobile car wash machines adheres.
- the above-described ventilation filter is contacted even with a small amount of oil or surfactant, the water resistance and air permeability of the filter are almost lost, and the originally required waterproofness and air permeability cannot be obtained. Therefore, in applications where there is a high risk of oil or surfactant adhering, air-permeable filters with oil repellency and waterproof properties are used.
- a PTFE base material coated with a fluoropolymer having a perfluoroalkyl group (hereinafter referred to as “RF group”) is known.
- RF group a fluoropolymer having a perfluoroalkyl group
- position ⁇ is a hydrogen atom or a methyl group
- a fluorine-containing polymer obtained by polymerizing alkyl acrylates or alkyl methacrylates having R F group is known (Patent Document 1).
- the fluoropolymer it is known to use a polymer having an R F group having 8 or more carbon atoms.
- a fluoropolymer having an R 8 F group having 8 or more carbon atoms is concerned in that it may be decomposed in the environment or in the living body and the decomposition products may accumulate, that is, the environmental load is high. Therefore, having a R F group having 6 or less carbon atoms, it is required to use a fluorine-containing polymer having no R F group having 8 or more carbon atoms.
- the present invention provides an oil-repellent waterproof breathable filter that has a low environmental load and has excellent liquid repellency against ketone solvents and ester solvents, and a method for producing the same.
- Oil repellent waterproof breathable filter of the present invention includes a base having a continuous porous structure, a oil-repellent waterproof air-permeable filter which is coated with a coating material comprising a fluorine-containing polymer having an R F group, the free
- the fluoropolymer has a constitutional unit based on the following monomer (a), and the proportion of the constitutional unit is 40 to 100% by mass in all constitutional units.
- the monomeric (a), a position ⁇ is a chlorine atom, is preferably an acrylate having an R F group having 6 carbon atoms.
- the said base material consists of PTFE.
- a substrate having a continuous porous structure, treated with oil-repellent waterproofing composition comprising a coating material and a medium comprising a fluorine-containing polymer having an R F group
- the fluoropolymer has a structural unit based on the following monomer (a), and the proportion of the structural unit is 40 to 100% by mass in all the structural units. It is characterized by being.
- the base material is preferably made of PTFE.
- the medium is preferably at least one selected from the group consisting of hydrofluorocarbons and hydrofluoroethers.
- the oil-repellent waterproof breathable filter of the present invention has a small environmental load and has excellent liquid repellency against ketone solvents and ester solvents. Moreover, according to the method for producing an oil-repellent waterproof breathable filter of the present invention, an oil-repellent waterproof breathable filter having a small environmental load and excellent liquid repellency with respect to a ketone solvent and an ester solvent can be obtained.
- a compound represented by the formula (1) is referred to as a compound (1).
- (meth) acrylate in the present specification means acrylate or methacrylate, and the same applies to other compounds.
- the monomer in this specification means the compound which has a polymerizable unsaturated group.
- the R F group in the present specification is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
- Oil repellent waterproof breathable filter of the present invention includes a base having a continuous porous structure, a filter is coated with a coating material comprising a fluorine-containing polymer having an R F group, the fluorine-containing polymer, It has a constitutional unit based on the monomer (a) described later, and the proportion of the constitutional unit is 40 to 100% by mass in all constitutional units (hereinafter referred to as “fluorine-containing polymer (A)”). .).
- the base material having a continuous porous structure in the present invention is a base material made of a gas permeable material and may be any material that allows gas, particularly air, to pass therethrough.
- the gas permeable material may be any of natural and synthetic materials, such as woven fabric, knitted fabric, non-woven fabric, net, felt, porous polymer sheet, cellulose paper, glass fiber paper, or a composite product combining these appropriately. Can be mentioned.
- a form of the substrate a sheet form, a tube form, and a plug form are preferable.
- the continuous porous structure of the substrate those having continuous pores penetrating both surfaces of the substrate are preferable. Examples thereof include a net shape, a mesh shape, and a porous shape.
- the material for the porous polymer sheet examples include polyethylene, polypropylene, polystyrene, polyimide, a fluorine-containing resin, and the like. From the viewpoint of excellent waterproofness, a fluorine-containing resin is preferable, and PTFE is more preferable.
- a porous PTFE sheet is preferable because it is excellent in drip-proof property, and can easily give air permeability to the inside and outside of an electric device while preventing intrusion of water droplets, oil droplets and dust, and a stretched porous PTFE sheet is preferable. Particularly preferred.
- the stretched porous PTFE sheet is obtained by mixing a PTFE fine powder with a molding aid to obtain a paste molded body, then removing the molding aid from the molded body, stretching at a high temperature and a high speed, and further if necessary. Obtained by firing.
- the stretched porous PTFE sheet may be a uniaxially stretched porous PTFE sheet or a biaxially stretched porous PTFE sheet.
- the microstructure of the stretched porous PTFE sheet is composed of fine fibrils called fibrils and granular nodules called nodes connecting these fibrils, and there are very fine pores between the fibrils and the nodes. They exist in a mutually continuous state, forming a so-called continuous porous structure.
- the nodes folded crystals
- the fibrils folded crystals are unwound by stretching so as to connect the nodes.
- the drawn linear molecular bundle is oriented in the stretching direction.
- a space defined between the fibrils or between the fibrils and the nodes is a fibrous structure having pores.
- the base material preferably has sufficient strength to be used alone (in a single layer) as a stretched porous PTFE sheet, but the stretched porous PTFE sheet is made of a stretchable breathable material such as a net such as a nonwoven fabric, a woven fabric or a knitted fabric. It may be used by laminating with a reinforcing layer.
- the galley number of the substrate is preferably 1,000 seconds or less, and more preferably 600 seconds or less.
- the substrate is an expanded porous PTFE sheet, a sheet having a pore diameter of 0.01 to 15 ⁇ m is preferable.
- Various additives such as an ultraviolet stabilizer, a colorant, a plasticizer, an antistatic agent, and an antibacterial agent may be added to the substrate within a range that does not adversely affect the substrate.
- a coating material is present so as to cover the substrate, but the thickness of the coating film of the coating material with respect to the hole diameter of the substrate is small, and there is a space even when the coating material is coated. It still exists and maintains a continuous porous structure.
- the fluorinated polymer (A) essentially comprises a structural unit based on the monomer (a) (hereinafter referred to as “unit ( ⁇ )”), and if necessary, a structural unit based on the monomer (b). (Hereinafter referred to as “unit ( ⁇ )”) and a structural unit based on the monomer (c) (hereinafter referred to as “unit ( ⁇ )”).
- the monomer (a) is an acrylate having a chlorine atom at the ⁇ -position and having an R F group having 1 to 6 carbon atoms.
- the monomer (a) the following compound (1) is preferable.
- Z is an R F group having 1 to 6 carbon atoms (provided that the R F group may contain an etheric oxygen atom).
- Examples of Z include the following groups. F (CF 2) 4 -, F (CF 2 ) 5- , F (CF 2 ) 6- , (CF 3 ) 2 CF (CF 2 ) 2 -etc.
- Y is a divalent organic group (excluding a perfluoroalkylene group) or a single bond.
- the divalent organic group an alkylene group is preferable.
- the alkylene group may be linear or branched.
- Examples of Y include the following groups. —CH 2 —, —CH 2 CH 2 — -(CH 2 ) 3- , -CH 2 CH 2 CH (CH 3 )-, —CH ⁇ CH—CH 2 —, -S-CH 2 CH 2- , —CH 2 CH 2 —S—CH 2 CH 2 —, —CH 2 CH 2 —SO 2 —CH 2 CH 2 —, —W—OC (O) NH—A—NHC (O) O— (C p H 2p ) — and the like.
- p is an integer of 2 to 30.
- A is an unbranched contrasting alkylene group, arylene group or aralkylene group, and —C 6 H 12 —, — ⁇ —CH 2 — ⁇ —, — ⁇ — (where ⁇ is a phenylene group).
- W is any of the following groups. —SO 2 N (R 1 ) —C d H 2d —, -CONHC d H 2d -, —CH (R F1 ) —C e H 2e —, -C q H 2q- .
- R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- d is an integer of 2 to 8
- R F1 is an R F group having 1 to 20 carbon atoms
- e is It is an integer from 0 to 6
- q is an integer from 1 to 20.
- R F1 is preferably an R F group having 1 to 6 carbon atoms, and more preferably an R F group having 4 or 6 carbon atoms.
- the compound (1) polymerizability with other monomers, flexibility of the film containing the fluoropolymer (A), adhesion of the fluoropolymer (A) to the substrate, solubility in the medium, From the viewpoint of ease of polymerization and the like, ⁇ -chloroacrylates having 4 to 6 carbon R F groups are preferred, and ⁇ -chloroacrylates having 6 C carbon R F groups are more preferred.
- Z is an R F group having 4 to 6 carbon atoms
- Y is a compound more preferably an alkylene group having 1 to 4 carbon atoms
- Z is at R F group having 6 carbon atoms
- a compound in which Y is an alkylene group having 1 to 4 carbon atoms is particularly preferred.
- a monomer (a) may be used individually by 1 type, and may use 2 or more types together.
- the monomer (b) is an acrylate having a hydrogen atom or a methyl group at the ⁇ -position and having an R F group having 1 to 6 carbon atoms. If the monomer (b) is used, the film-forming property of the fluoropolymer (A) is improved, and the liquid repellency after coating the coating material containing the fluoropolymer (A) is improved.
- Examples of the monomer (b) include the same monomers as those described for the monomer (a) except that the ⁇ -position is a hydrogen atom or a methyl group.
- Preferable monomer (b) is the same as preferable monomer (a) except that the ⁇ -position is a hydrogen atom or a methyl group, and the following compound (2) is particularly preferable.
- Z 1 is an R 4 F group having 4 to 6 carbon atoms
- Y 1 is an alkylene group having 1 to 4 carbon atoms
- R is a hydrogen atom or a methyl group.
- a monomer (b) may be used individually by 1 type, and may use 2 or more types together.
- the monomer (c) is a monomer other than the monomer (a) and the monomer (b), and is a monomer copolymerizable with the monomer (a) and the monomer (b). It is. If monomer (c) is used, the adhesiveness to the base material of the film
- a monomer (c) may be used individually by 1 type, and may use 2 or more types together.
- the proportion of the unit ( ⁇ ) in the fluoropolymer (A) is 40 to 100% by mass, preferably 55 to 100% by mass, more preferably 70 to 100% by mass, and particularly 100% by mass in all the structural units. preferable. When the ratio of the unit ( ⁇ ) is at least the lower limit, excellent liquid repellency with respect to the ketone solvent and the ester solvent can be obtained.
- the proportion of the unit ( ⁇ ) in the fluoropolymer (A) is preferably 0 to 60% by mass and more preferably 0 to 30% by mass in all the structural units. A ratio of the unit ( ⁇ ) of 0% by mass means that the unit ( ⁇ ) is not included.
- the unit ( ⁇ ) ratio is preferably 10% by mass or more in that the glass transition temperature is lowered and the film-forming property at a low temperature is excellent.
- the proportion of the unit ( ⁇ ) in the fluoropolymer (A) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and particularly preferably 0% by mass in all the structural units.
- the proportion of structural units based on monomers in the present invention is determined from NMR analysis and elemental analysis. In addition, when it cannot obtain
- the number average molecular weight (Mn) of the fluoropolymer (A) is preferably from 1,000 to 200,000, more preferably from 10,000 to 50,000.
- the number average molecular weight (Mn) of the fluorinated polymer (A) is at least the lower limit, the liquid repellency with respect to the ketone solvent and the ester solvent is improved.
- the number average molecular weight (Mn) of the fluorinated polymer (A) is not more than the above upper limit, the film-forming property becomes good, and as a result, sufficient liquid repellency with respect to the ketone solvent and the ester solvent is obtained.
- the number average molecular weight (Mn) of the fluoropolymer (A) is a molecular weight in terms of polymethyl methacrylate, which is measured by gel permeation chromatography (GPC).
- the fluorine-containing polymer (A) is produced by polymerizing the monomer (a), the monomer (b) and the monomer (c) used as necessary.
- Examples of the polymerization method include solution polymerization in a fluorine-based medium, emulsion polymerization in an aqueous medium, suspension polymerization in an aqueous medium, and the like, and solution polymerization in a fluorine-based medium is preferable.
- the polymerization initiator examples include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a water-soluble or oil-soluble radical polymerization initiator is preferable.
- a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature.
- an azo compound is particularly preferable.
- the polymerization temperature is preferably 30 to 80 ° C.
- the addition amount of the polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used for the polymerization.
- the proportion of the monomer (a) is 40 to 100% by mass from the viewpoint of liquid repellency with respect to the ketone solvent and the ester solvent among the total monomers (100% by mass) used in the polymerization. To 100% by mass is preferable, 70 to 100% by mass is more preferable, and 100% by mass is particularly preferable.
- the proportion of the monomer (b) is preferably 0 to 60% by mass, more preferably 0 to 45% by mass, and particularly preferably 0 to 30% by mass, based on the total monomer (100% by mass) used in the polymerization. preferable.
- the proportion of the monomer (c) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and particularly preferably 0% by mass, based on the total monomer (100% by mass) used in the polymerization.
- the coating material that covers the base material of the oil-repellent waterproof breathable filter of the present invention may contain a fluorine-containing polymer other than the fluorine-containing polymer (A).
- the fluorine-containing polymer other than the fluoropolymer (A), the fluorine-containing polymer having an R F group other than the fluoropolymer (A) (hereinafter, referred to as "fluorine-containing polymer (B)”.)
- fluorine-containing polymer (C) a fluorine-containing polymer having a fluorine-containing aliphatic ring structure in the main chain
- the fluorine-containing polymer (B) has the unit ( ⁇ ), and the proportion of the unit ( ⁇ ) is less than 40% by mass in all the structural units, or the unit ( ⁇ ).
- the fluoropolymer having the unit ( ⁇ ) as an essential component and the unit ( ⁇ ) as required is preferable.
- the number average molecular weight (Mn) of the fluoropolymer (B) is preferably from 1,000 to 200,000, more preferably from 5,000 to 50,000.
- the number average molecular weight (Mn) of the fluoropolymer (B) is not less than the lower limit, the liquid repellency with respect to the ketone solvent and the ester solvent is improved. If the number average molecular weight (Mn) of the fluoropolymer (B) is not more than the above upper limit value, the film-forming property will be good, and as a result, sufficient liquid repellency for ketone solvents and ester solvents will be obtained.
- the number average molecular weight (Mn) of the fluoropolymer (B) is a molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography (GPC).
- the fluoropolymer (B) can be produced by the same method as the fluoropolymer (A) except for the amount of the monomer (a), monomer (b) and monomer (c) used.
- Fluoropolymer (C) As the fluorinated polymer (C), a fluorinated polymer obtained by polymerizing a monomer having a fluorinated ring structure, or a fluorinated monomer having at least two polymerizable double bonds is cyclized. A fluoropolymer having a ring structure in the main chain obtained by polymerization is preferred. Examples of these fluoropolymers include the polymers described in Japanese Patent No. 2854223.
- the proportion of the fluoropolymer (B) is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (A).
- the proportion of the fluoropolymer (C) is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (A).
- the oil-repellent waterproof breathable filter of the present invention comprises an oil-repellent waterproof agent composition comprising a base material having a continuous porous structure, a coating material containing the above-mentioned fluoropolymer (A) as an essential component, and a medium. Manufactured by a method of processing and removing the media.
- the medium of the oil repellent waterproofing agent composition is preferably a fluorine-based medium, more preferably hydrofluorocarbon (hereinafter referred to as “HFC”) or hydrofluoroether (hereinafter referred to as “HFE”).
- HFC is a compound composed of only carbon atoms, hydrogen atoms, and fluorine atoms, in which part of hydrocarbon hydrogen atoms is replaced by fluorine atoms.
- the HFC is preferably an HFC that has 4 or more carbon atoms and is liquid at normal temperature and pressure.
- HFE is a compound containing an etheric oxygen atom between carbon-carbon atoms of HFC.
- HFE is preferably HFE having 4 or more carbon atoms and liquid at normal temperature and pressure.
- the normal temperature and normal pressure in this specification means 25 ° C. and 1 atm.
- the molecular structure of HFC and HFE may be linear or branched, and is preferably linear.
- the number of etheric oxygen atoms contained in one HFE molecule may be one or two or more. One or two is preferable and one is more preferable from the viewpoint of a boiling point that is easy to use as a medium and stability.
- HFC include the following compounds. 1,1,1,3,3-pentafluorobutane (CF 3 CH 2 CF 2 CH 3 ), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (CF 3 CF 2 CHFCHFCF 3 ), 1H-monodecafluoropentane (C 5 F 11 H), 3H-monodecafluoropentane (C 5 F 11 H), 1H-tridecafluorohexane (C 6 F 13 H), 1H-pentadecafluoroheptane (C 7 F 15 H), 3H-pentadecafluoroheptane (C 7 F 15 H), 1H-heptadecafluorooctane (C 8 F 17 H), 1H-nonadecafluorononane (C 9 F 19 H), 1H-perfluorodecane (C 10 F 21 H), 1,1,1,2,2,3,3,4,4-nonafluorohexane (CF 3
- 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane and 1H-tridecafluorohexane are preferable.
- 2,2,3,3,4,4,5,5,6,6-tridecafluorooctane is more preferred.
- HFE include the following compounds. Methyl perfluorobutyl ether (C 4 F 9 OCH 3 ), Ethyl perfluorobutyl ether (C 4 F 9 OCH 2 CH 3 ), Methyl perfluoropentyl ether (C 5 F 11 OCH 3 ), Ethyl perfluoropentyl ether (C 5 F 11 OCH 2 CH 3 ), Methyl perfluorohexyl ether (C 6 F 13 OCH 3 ), Ethyl perfluorohexyl ether (C 6 F 13 OCH 2 CH 3 ), Methyl perfluoroheptyl ether (C 7 F 15 OCH 3 ), Ethyl perfluoro to Petit ether (C 7 F 15 OCH 2 CH 3), Methyl perfluorooctyl ether (C 8 F 17 OCH 3 ), Ethyl perfluorooctyl ether (C 8 F 17 OCH 2 CH 3 ),
- methyl perfluorohexyl ether ethyl perfluorobutyl ether, and methyl perfluorobutyl ether are preferable, and methyl perfluorohexyl ether is more preferable.
- a medium may be used individually by 1 type and may use 2 or more types together.
- the medium used for the polymerization of the fluoropolymer (A) or the like may be diluted as necessary.
- the ratio of the medium is preferably 100 to 50,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to the total amount (100 parts by mass) of the fluoropolymers (A) to (C). If the ratio of the medium is equal to or higher than the lower limit value, the processing efficiency is improved. If the ratio of the medium is not more than the above upper limit value, the medium removal efficiency is improved.
- Examples of the method for treating the substrate with the oil repellent waterproofing agent composition include dip coating and spray coating.
- Examples of the method for removing the medium include a method of evaporating the medium by air drying or heat treatment.
- the temperature for removing the medium is preferably 50 to 200 ° C., and more preferably 100 to 150 ° C. from the viewpoint of improving oil repellency.
- the base material having a continuous porous structure is coated with a coating material containing the fluoropolymer (A), so that the ketone solvent and Excellent liquid repellency against ester solvents. Further, without using a monomer having 8 or more R F group carbon, since sufficient liquid repellency against ketone solvent and ester solvent is obtained, environmental load can be reduced.
- the oil repellent waterproof breathable filter of the present invention has sufficient oil repellency and water repellency.
- the fluorine weight fraction of the fluorinated polymer is in accordance with the combustion and pyrohydrolysis method (combustion conditions are M. Noshiro, T. Yarita, Japan analyst 1977, 26, 721-723).
- Example 2 20 g of perfluoroalkyl methacrylate (CH 2 ⁇ CCH 3 COOCH 2 CH 2 C 6 F 13 ) (hereinafter referred to as “C6FMA”) as the monomer (b), 46.7 g of Asahiclin AK-225, and As a polymerization initiator, 0.11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours.
- C6FMA perfluoroalkyl methacrylate
- As a polymerization initiator 0.11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours.
- Example 3 8 g of ⁇ -ClC6FA as the monomer (a), 72 g of Asahiklin AC-6000 (Asahi Glass Co., Ltd., C 6 F 13 C 2 H 5 , fluorine weight fraction: 71.0 mass%), and polymerization start As an agent, 0.24 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A2 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A2 was 17,000.
- Example 4 7.2 g of monomer (a) ⁇ -ClC6FA, 0.8 g of C6FMA monomer (b), 72 g of Asahiklin AC-6000, and 2,2′-azobis ( 0.24 g of 2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A3 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A3 was 17,000.
- Example 5 4.8 g of monomer (a) ⁇ -ClC6FA, 3.2 g of monomer (b) C6FMA, 72 g of Asahiklin AC-6000, and 2,2′-azobis ( 0.24 g of 2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A4 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A4 was 15,000.
- Cytop CTX-109AE (Asahi Glass Co., Ltd., (C 6 F 10 O) n , fluorine weight fraction: 68.3 mass%) is put in a PTFE container and dried at 200 ° C. for 1 hour to form a main chain.
- a fluorinated polymer C1 having a fluorinated aliphatic ring structure was obtained.
- Table 1 shows the monomer compositions of Examples 1 to 6 and the number average molecular weights (Mn) of the fluoropolymers.
- Example 8 An oil repellent waterproofing agent composition was prepared by dissolving 2.0 parts of the fluoropolymer A1 obtained in Example 1 in 100 parts of the medium Asahiclin AC-6000 (HFC). Thereafter, the stretched porous PTFE sheet (pore diameter: 1 ⁇ m, thickness: 300 ⁇ m, porosity: 60% (both nominal values)) as a base material is applied to the oil repellent waterproofing composition by dip coating (pickup speed: 5 mm / second). Sample 1 was obtained by removing the medium by drying at 150 ° C. for 10 minutes. About the obtained sample 1, the wettability test was done.
- Example 9 1.98 parts of the fluorinated polymer A1 obtained in Example 1 and 0.02 part of the fluorinated polymer C1 obtained in Example 7 were dissolved in 100 parts of the medium ASAHIKLIN AC-6000 to make the oil repellent.
- Sample 2 was prepared in the same manner as in Example 8 except that the waterproofing agent composition was prepared. About the obtained sample 2, the wettability test was done.
- Example 10 Except for preparing an oil repellent waterproofing composition by dissolving 2.0 parts of the fluoropolymer B1 obtained in Example 2 in 100 parts of the medium Asahiclin AC-6000, the same procedure as in Example 8 was performed. Sample 3 was prepared. The obtained sample 3 was subjected to a wettability test.
- Example 11 1.98 parts of the fluoropolymer B1 obtained in Example 2 and 0.02 part of the fluoropolymer C1 obtained in Example 7 were dissolved in 100 parts of the medium Asahiclin AC-6000 to make the oil repellent.
- Sample 4 was prepared in the same manner as in Example 8 except that the waterproofing agent composition was prepared. The obtained sample 4 was subjected to a wettability test.
- Example 12 The stretched porous PTFE sheet as the base material was used as a sample 5 untreated, and a wettability test was performed.
- Example 10 and Example 11 not coated with the fluoropolymer (A) had poor liquid repellency against acetone and MEK, whereas Example 8 coated with the fluoropolymer (A). And the sample of Example 9 was excellent in liquid repellency against all of n-hexane, n-decane, ethanol, acetone and MEK.
- Example 13 Except that an oil repellent waterproofing agent composition was prepared by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A2 obtained in Example 3 to prepare an oil repellent waterproofing composition. Sample 6 was obtained in the same manner. The obtained sample 6 was subjected to a wettability test.
- Example 14 Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A3 obtained in Example 4, and preparing an oil repellent waterproofing composition. Sample 7 was obtained in the same manner. About the obtained sample 7, the wettability test was done.
- Example 15 Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A4 obtained in Example 5, and preparing an oil repellent waterproofing composition. Sample 8 was obtained in the same manner. The obtained sample 8 was subjected to a wettability test.
- Example 16 Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of the 10% by mass solution of the fluoropolymer B2 obtained in Example 6, and preparing an oil repellent waterproofing agent composition. Sample 9 was obtained in the same manner. About the obtained sample 9, the wettability test was done. The results of the wettability test in Example 10 and Examples 13 to 16 are shown in Table 3.
- Example 16 using only the fluoropolymer (B) having a unit ratio based on the monomer (a) of less than 40% by mass has poor liquid repellency against MEK
- Examples 13 to 15 using the fluoropolymer (A) having a unit ratio based on the monomer (a) of 40% by mass or more are based on n-hexane, n-decane, ethanol, acetone and MEK. Excellent liquid repellency.
- Example 17 10 g of the 10% by mass solution of the fluoropolymer A2 obtained in Example 3 was added to a 500 mL glass flask containing 200 g of methanol while stirring, and then the supernatant was removed by decantation. A solid containing polymer A2 was obtained. Then, 0.9g of fluoropolymer A2 (number average molecular weight 17,000) which has a perfluoroalkyl group was obtained by drying this solid substance. 2.0 parts of the obtained fluorinated polymer A2 was dissolved in 100 parts of HFE-7300 (manufactured by Sumitomo 3M, C 6 F 13 OCH 3 , fluorine weight fraction: 70.6 mass%) to make it oil repellent. A waterproofing agent composition was prepared. Sample 10 was obtained in the same manner as Example 8 using the obtained oil repellent waterproofing composition. About the obtained sample 10, the wettability test was done.
- Example 18 Oil repellent waterproofing agent in the same manner as in Example 17 except that the 10% by mass solution of the fluoropolymer A3 obtained in Example 4 was used instead of the 10% by mass solution of the fluoropolymer A2 obtained in Example 3. A composition was prepared. Then, the sample 11 was obtained like Example 8 using the obtained oil-repellent waterproofing agent composition. About the obtained sample 11, the wettability test was done. Table 4 shows the results of the wettability test in Examples 17 and 18.
- Example 19 An oil repellent waterproofing composition was prepared by adding 80 parts of Asahiclin AC-6000 to 20 parts of the 10% by mass solution of the fluoropolymer A1 obtained in Example 1 and diluting. Thereafter, the glass substrate was treated with the oil repellent waterproofing agent composition by dip coating (pickup speed: 5 mm / second), and dried at 150 ° C. for 1 hour to obtain Sample 12. The obtained sample 12 was subjected to contact angle measurement (after 1 second and after 21 seconds).
- Example 20 A sample 13 was obtained in the same manner as in Example 19 except that the 10% by mass solution of the fluoropolymer B1 obtained in Example 2 was used instead of the 10% by mass solution of the fluoropolymer A1 obtained in Example 1. It was. The obtained sample 13 was subjected to contact angle measurement.
- the contact angle of the test liquid (ethyl acetate, butyl acetate, MEK, water, n-decane) was measured according to the following apparatus and conditions.
- Example 20 in which the fluoropolymer (A) was not used, the contact angle after 21 seconds after dropping was small and the liquid repellency was poor, whereas the fluoropolymer ( In Example 19 using A), excellent liquid repellency was exhibited for both ethyl acetate and butyl acetate as ester solvents and MEK as a ketone solvent.
- the oil-repellent waterproof breathable filter of the present invention is useful as a filter used for an exhaust gas sensor of an automobile, an ink cartridge of an inkjet printer, and the like.
- the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2010-286666 filed on Dec. 22, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Filtering Materials (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
単量体(a):α位が塩素原子であり、炭素数1~6のRF基を有するアクリレート。 Oil repellent waterproof breathable filter of the present invention includes a base having a continuous porous structure, a oil-repellent waterproof air-permeable filter which is coated with a coating material comprising a fluorine-containing polymer having an R F group, the free The fluoropolymer has a constitutional unit based on the following monomer (a), and the proportion of the constitutional unit is 40 to 100% by mass in all constitutional units.
Monomer (a): An acrylate having a chlorine atom at the α-position and an R F group having 1 to 6 carbon atoms.
また、前記基材がPTFEからなることが好ましい。 Oil repellent waterproof breathable filter of the present invention, the monomeric (a), a position α is a chlorine atom, is preferably an acrylate having an R F group having 6 carbon atoms.
Moreover, it is preferable that the said base material consists of PTFE.
単量体(a):α位が塩素原子であり、炭素数1~6のRF基を有するアクリレート。 Method for producing oil repellent waterproof breathable filter of the present invention, a substrate having a continuous porous structure, treated with oil-repellent waterproofing composition comprising a coating material and a medium comprising a fluorine-containing polymer having an R F group In the method for removing the medium, the fluoropolymer has a structural unit based on the following monomer (a), and the proportion of the structural unit is 40 to 100% by mass in all the structural units. It is characterized by being.
Monomer (a): An acrylate having a chlorine atom at the α-position and an R F group having 1 to 6 carbon atoms.
また、前記媒体が、ハイドロフルオロカーボンおよびハイドロフルオロエーテルからなる群から選ばれる1種以上であることが好ましい。 In the method for producing an oil-repellent waterproof breathable filter of the present invention, the base material is preferably made of PTFE.
The medium is preferably at least one selected from the group consisting of hydrofluorocarbons and hydrofluoroethers.
また、本発明の撥油防水性通気フィルタの製造方法によれば、環境負荷が小さく、かつケトン系溶剤およびエステル系溶剤に対する撥液性が優れた撥油防水性通気フィルタが得られる。 The oil-repellent waterproof breathable filter of the present invention has a small environmental load and has excellent liquid repellency against ketone solvents and ester solvents.
Moreover, according to the method for producing an oil-repellent waterproof breathable filter of the present invention, an oil-repellent waterproof breathable filter having a small environmental load and excellent liquid repellency with respect to a ketone solvent and an ester solvent can be obtained.
本発明の撥油防水性通気フィルタは、連続多孔質構造を有する基材が、RF基を有する含フッ素重合体を含む被覆材料によって被覆されたフィルタであって、前記含フッ素重合体が、後述する単量体(a)に基づく構成単位を有し、該構成単位の割合が全構成単位において40~100質量%の含フッ素重合体(以下、「含フッ素重合体(A)」と記す。)であることを特徴とする。 <Oil-repellent waterproof breathable filter>
Oil repellent waterproof breathable filter of the present invention includes a base having a continuous porous structure, a filter is coated with a coating material comprising a fluorine-containing polymer having an R F group, the fluorine-containing polymer, It has a constitutional unit based on the monomer (a) described later, and the proportion of the constitutional unit is 40 to 100% by mass in all constitutional units (hereinafter referred to as “fluorine-containing polymer (A)”). .).
本発明における連続多孔質構造を有する基材は、気体透過性材料からなる基材であり、気体、特に空気を通すものであればよい。気体透過性材料としては、天然、合成素材のいずれでもよく、織布、編布、不織布、ネット、フェルト、多孔質ポリマーシート、セルロース紙、ガラス繊維紙、またはこれらを適宜組み合せた複合品等が挙げられる。
基材の形態としては、シート状、チューブ状、プラグ型が好ましい。
基材の連続多孔質構造としては、基材の両面に貫通する連続孔を有するものが好ましい。例えば、ネット状、メッシュ状、多孔質等が挙げられる。 [Base material]
The base material having a continuous porous structure in the present invention is a base material made of a gas permeable material and may be any material that allows gas, particularly air, to pass therethrough. The gas permeable material may be any of natural and synthetic materials, such as woven fabric, knitted fabric, non-woven fabric, net, felt, porous polymer sheet, cellulose paper, glass fiber paper, or a composite product combining these appropriately. Can be mentioned.
As a form of the substrate, a sheet form, a tube form, and a plug form are preferable.
As the continuous porous structure of the substrate, those having continuous pores penetrating both surfaces of the substrate are preferable. Examples thereof include a net shape, a mesh shape, and a porous shape.
延伸多孔質PTFEシートは、PTFEのファインパウダーを成形助剤と混合してペーストの成形体を得た後、該成形体から成形助剤を除去し、高温高速度で延伸し、さらに必要に応じて焼成することにより得られる。延伸多孔質PTFEシートは、一軸延伸多孔質PTFEシートであってもよく、二軸延伸多孔質PTFEシートであってもよい。 Examples of the material for the porous polymer sheet include polyethylene, polypropylene, polystyrene, polyimide, a fluorine-containing resin, and the like. From the viewpoint of excellent waterproofness, a fluorine-containing resin is preferable, and PTFE is more preferable. As the base material, a porous PTFE sheet is preferable because it is excellent in drip-proof property, and can easily give air permeability to the inside and outside of an electric device while preventing intrusion of water droplets, oil droplets and dust, and a stretched porous PTFE sheet is preferable. Particularly preferred.
The stretched porous PTFE sheet is obtained by mixing a PTFE fine powder with a molding aid to obtain a paste molded body, then removing the molding aid from the molded body, stretching at a high temperature and a high speed, and further if necessary. Obtained by firing. The stretched porous PTFE sheet may be a uniaxially stretched porous PTFE sheet or a biaxially stretched porous PTFE sheet.
基材は、延伸多孔質PTFEシート単独で(単層で)使用できるだけの強度を有することが好ましいが、延伸多孔質PTFEシートを、不織布、織物や編物等のネット等、伸縮性を持つ通気性の補強層と積層して使用してもよい。 The microstructure of the stretched porous PTFE sheet is composed of fine fibrils called fibrils and granular nodules called nodes connecting these fibrils, and there are very fine pores between the fibrils and the nodes. They exist in a mutually continuous state, forming a so-called continuous porous structure. Specifically, in the case of uniaxial stretching, the nodes (folded crystals) are thin islands perpendicular to the stretching direction, and the fibrils (folded crystals are unwound by stretching) so as to connect the nodes. The drawn linear molecular bundle is oriented in the stretching direction. A space defined between the fibrils or between the fibrils and the nodes is a fibrous structure having pores. In the case of biaxial stretching, the fibrils spread radially, the nodes connecting the fibrils are scattered in islands, and a spider web-like fibrous structure with many spaces defined by the fibrils and the nodes exists. ing.
The base material preferably has sufficient strength to be used alone (in a single layer) as a stretched porous PTFE sheet, but the stretched porous PTFE sheet is made of a stretchable breathable material such as a net such as a nonwoven fabric, a woven fabric or a knitted fabric. It may be used by laminating with a reinforcing layer.
基材には、悪影響を及ぼさない範囲内で、紫外線安定剤、着色剤、可塑剤、静電防止剤、抗菌剤等の各種の添加剤が添加されていてもよい。 The galley number of the substrate (measurement method and the like conforms to JIS P8117) is preferably 1,000 seconds or less, and more preferably 600 seconds or less. When the substrate is an expanded porous PTFE sheet, a sheet having a pore diameter of 0.01 to 15 μm is preferable.
Various additives such as an ultraviolet stabilizer, a colorant, a plasticizer, an antistatic agent, and an antibacterial agent may be added to the substrate within a range that does not adversely affect the substrate.
(含フッ素重合体(A))
含フッ素重合体(A)は、単量体(a)に基づく構成単位(以下、「単位(α)」と記す。)を必須とし、必要に応じて単量体(b)に基づく構成単位(以下、「単位(β)」と記す。)、単量体(c)に基づく構成単位(以下、「単位(γ)」と記す。)を有する。
単量体(a)は、α位が塩素原子であり、炭素数1~6のRF基を有するアクリレートである。単量体(a)としては、下記化合物(1)が好ましい。
(Z-Y)-OC(O)CCl=CH2 ・・・(1)。 [Coating material]
(Fluoropolymer (A))
The fluorinated polymer (A) essentially comprises a structural unit based on the monomer (a) (hereinafter referred to as “unit (α)”), and if necessary, a structural unit based on the monomer (b). (Hereinafter referred to as “unit (β)”) and a structural unit based on the monomer (c) (hereinafter referred to as “unit (γ)”).
The monomer (a) is an acrylate having a chlorine atom at the α-position and having an R F group having 1 to 6 carbon atoms. As the monomer (a), the following compound (1) is preferable.
(ZY) —OC (O) CCl═CH 2 (1).
F(CF2)4-、
F(CF2)5-、
F(CF2)6-、
(CF3)2CF(CF2)2-等。 Z is an R F group having 1 to 6 carbon atoms (provided that the R F group may contain an etheric oxygen atom). Examples of Z include the following groups.
F (CF 2) 4 -,
F (CF 2 ) 5- ,
F (CF 2 ) 6- ,
(CF 3 ) 2 CF (CF 2 ) 2 -etc.
2価有機基としては、アルキレン基が好ましい。アルキレン基は、直鎖状であってもよく、分岐状であってもよい。さらに、2価有機基には、アルキレン基と共に、-O-、-NH-、-CO-、-S-、-SO2-、-CD1=CD2-(ただし、D1、D2は、それぞれ独立に水素原子またはメチル基である。)等を有していてもよい。 Y is a divalent organic group (excluding a perfluoroalkylene group) or a single bond.
As the divalent organic group, an alkylene group is preferable. The alkylene group may be linear or branched. Further, the divalent organic group includes —O—, —NH—, —CO—, —S—, —SO 2 —, —CD 1 = CD 2 — (where D 1 and D 2 are And each independently a hydrogen atom or a methyl group.
-CH2-、
-CH2CH2-
-(CH2)3-、
-CH2CH2CH(CH3)-、
-CH=CH-CH2-、
-S-CH2CH2-、
-CH2CH2-S-CH2CH2-、
-CH2CH2-SO2-CH2CH2-、
-W-OC(O)NH-A-NHC(O)O-(CpH2p)-等。
ただし、pは、2~30の整数である。
Aは、分岐のない対照的なアルキレン基、アリレン基またはアラルキレン基であり、-C6H12-、-φ-CH2-φ-、-φ-(ただし、φはフェニレン基である。)が好ましい。
Wは、下記の基のいずれかである。
-SO2N(R1)-CdH2d-、
-CONHCdH2d-、
-CH(RF1)-CeH2e-、
-CqH2q-。
ただし、R1は、水素原子または炭素数1~4のアルキル基であり、dは、2~8の整数であり、RF1は、炭素数1~20のRF基であり、eは、0~6の整数であり、qは、1~20の整数である。RF1としては、炭素数1~6のRF基が好ましく、炭素数4または6のRF基がより好ましい。 Examples of Y include the following groups.
—CH 2 —,
—CH 2 CH 2 —
-(CH 2 ) 3- ,
-CH 2 CH 2 CH (CH 3 )-,
—CH═CH—CH 2 —,
-S-CH 2 CH 2- ,
—CH 2 CH 2 —S—CH 2 CH 2 —,
—CH 2 CH 2 —SO 2 —CH 2 CH 2 —,
—W—OC (O) NH—A—NHC (O) O— (C p H 2p ) — and the like.
However, p is an integer of 2 to 30.
A is an unbranched contrasting alkylene group, arylene group or aralkylene group, and —C 6 H 12 —, —φ—CH 2 —φ—, —φ— (where φ is a phenylene group). Is preferred.
W is any of the following groups.
—SO 2 N (R 1 ) —C d H 2d —,
-CONHC d H 2d -,
—CH (R F1 ) —C e H 2e —,
-C q H 2q- .
Where R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d is an integer of 2 to 8, R F1 is an R F group having 1 to 20 carbon atoms, and e is It is an integer from 0 to 6, and q is an integer from 1 to 20. R F1 is preferably an R F group having 1 to 6 carbon atoms, and more preferably an R F group having 4 or 6 carbon atoms.
また、化合物(1)としては、Zが炭素数4~6のRF基であり、Yが炭素数1~4のアルキレン基である化合物がさらに好ましく、Zが炭素数6のRF基であり、Yが炭素数1~4のアルキレン基である化合物が特に好ましい。特に好ましい化合物(1)の例として、ZがF(CF2)6-であり、Yが-CH2CH2-である、F(CF2)6-CH2CH2-OC(O)CCl=CH2が挙げられる。
単量体(a)は、1種を単独で使用してもよく、2種以上を併用してもよい。 As the compound (1), polymerizability with other monomers, flexibility of the film containing the fluoropolymer (A), adhesion of the fluoropolymer (A) to the substrate, solubility in the medium, From the viewpoint of ease of polymerization and the like, α-chloroacrylates having 4 to 6 carbon R F groups are preferred, and α-chloroacrylates having 6 C carbon R F groups are more preferred.
The compound (1), Z is an R F group having 4 to 6 carbon atoms, Y is a compound more preferably an alkylene group having 1 to 4 carbon atoms, Z is at R F group having 6 carbon atoms A compound in which Y is an alkylene group having 1 to 4 carbon atoms is particularly preferred. As an example of a particularly preferred compound (1), F (CF 2 ) 6 —CH 2 CH 2 —OC (O) CCl, wherein Z is F (CF 2 ) 6 — and Y is —CH 2 CH 2 —. = CH 2.
A monomer (a) may be used individually by 1 type, and may use 2 or more types together.
Z1-Y1-OC(O)CR=CH2 ・・・(2)。
ただし、Z1は、炭素数4~6のRF基であり、Y1は、炭素数1~4のアルキレン基であり、Rは水素原子またはメチル基である。
単量体(b)は、1種を単独で使用してもよく、2種以上を併用してもよい。 Examples of the monomer (b) include the same monomers as those described for the monomer (a) except that the α-position is a hydrogen atom or a methyl group. Preferable monomer (b) is the same as preferable monomer (a) except that the α-position is a hydrogen atom or a methyl group, and the following compound (2) is particularly preferable.
Z 1 —Y 1 —OC (O) CR═CH 2 (2).
However, Z 1 is an R 4 F group having 4 to 6 carbon atoms, Y 1 is an alkylene group having 1 to 4 carbon atoms, and R is a hydrogen atom or a methyl group.
A monomer (b) may be used individually by 1 type, and may use 2 or more types together.
単量体(c)としては、たとえば、RF基を有さない(メタ)アクリレート類、(メタ)アクリルアミド類、(メタ)アクリロニトリル類、ビニル類、オレフィン類等が挙げられる。具体的には、たとえば、下記の化合物が挙げられる。
2-エチルヘキシル(メタ)アクリレート、ステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、(メタ)アクリル酸、ポリオキシアルキレン(メタ)アクリレート、グリシジル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソシアナートエチル(メタ)アクリレート、アジリジニル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、ポリシロキサン部分を有する(メタ)アクリレート。
(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、メチロール化(メタ)アクリルアミド、酢酸ビニル、塩化ビニル、フッ化ビニル、ビニルアルキルエーテル、ハロゲン化アルキルビニルエーテル、ビニルアルキルケトン、N-ビニルカルバゾール、エチレン、ブタジエン、イソプレン、クロロプレン、スチレン、α-メチルスチレン、p-メチルスチレン、無水マレイン酸等。
単量体(c)は、1種を単独で使用してもよく、2種以上を併用してもよい。 The monomer (c) is a monomer other than the monomer (a) and the monomer (b), and is a monomer copolymerizable with the monomer (a) and the monomer (b). It is. If monomer (c) is used, the adhesiveness to the base material of the film | membrane containing a fluoropolymer (A) can improve, and cost can be reduced.
The monomer (c), for example, no R F group (meth) acrylates, (meth) acrylamides, (meth) acrylonitriles, vinyls, olefins, and the like. Specific examples include the following compounds.
2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, polyoxyalkylene (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, isocyanate ethyl ( (Meth) acrylate, aziridinyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylate having a polysiloxane moiety.
(Meth) acrylamide, diacetone (meth) acrylamide, methylolated (meth) acrylamide, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, N-vinyl carbazole, ethylene, butadiene, Isoprene, chloroprene, styrene, α-methylstyrene, p-methylstyrene, maleic anhydride and the like.
A monomer (c) may be used individually by 1 type, and may use 2 or more types together.
含フッ素重合体(A)における単位(β)の割合は、全構成単位において、0~60質量%が好ましく、0~30質量%がより好ましい。単位(β)の割合が0質量%とは、単位(β)を有さないことを意味する。単位(β)の割合が前記上限値以下であれば、ケトン系溶剤およびエステル系溶剤に対する撥液性に優れ、かつ造膜性に優れる。また、ガラス転移温度が低下し、低温での造膜性に優れる点では、単位(β)の割合は10質量%以上が好ましい。
含フッ素重合体(A)における単位(γ)の割合は、全構成単位において、0~30質量%が好ましく、0~10質量%がより好ましく、0質量%が特に好ましい。単位(γ)の割合が前記上限値以下であれば、ケトン系溶剤およびエステル系溶剤に対する撥液性に優れる。 The proportion of the unit (α) in the fluoropolymer (A) is 40 to 100% by mass, preferably 55 to 100% by mass, more preferably 70 to 100% by mass, and particularly 100% by mass in all the structural units. preferable. When the ratio of the unit (α) is at least the lower limit, excellent liquid repellency with respect to the ketone solvent and the ester solvent can be obtained.
The proportion of the unit (β) in the fluoropolymer (A) is preferably 0 to 60% by mass and more preferably 0 to 30% by mass in all the structural units. A ratio of the unit (β) of 0% by mass means that the unit (β) is not included. When the proportion of the unit (β) is not more than the above upper limit value, the liquid repellency with respect to the ketone solvent and the ester solvent is excellent, and the film forming property is excellent. In addition, the unit (β) ratio is preferably 10% by mass or more in that the glass transition temperature is lowered and the film-forming property at a low temperature is excellent.
The proportion of the unit (γ) in the fluoropolymer (A) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and particularly preferably 0% by mass in all the structural units. When the proportion of the unit (γ) is not more than the above upper limit value, the liquid repellency with respect to the ketone solvent and the ester solvent is excellent.
含フッ素重合体(A)の数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される、ポリメタクリル酸メチル換算の分子量である。 The number average molecular weight (Mn) of the fluoropolymer (A) is preferably from 1,000 to 200,000, more preferably from 10,000 to 50,000. When the number average molecular weight (Mn) of the fluorinated polymer (A) is at least the lower limit, the liquid repellency with respect to the ketone solvent and the ester solvent is improved. When the number average molecular weight (Mn) of the fluorinated polymer (A) is not more than the above upper limit, the film-forming property becomes good, and as a result, sufficient liquid repellency with respect to the ketone solvent and the ester solvent is obtained.
The number average molecular weight (Mn) of the fluoropolymer (A) is a molecular weight in terms of polymethyl methacrylate, which is measured by gel permeation chromatography (GPC).
ラジカル重合開始剤としては、アゾ系重合開始剤、過酸化物系重合開始剤、レドックス系開始剤等の汎用の開始剤が、重合温度に応じて使用される。ラジカル重合開始剤としては、アゾ系化合物が特に好ましい。重合温度は30~80℃が好ましい。
重合開始剤の添加量は、重合に使用する単量体の総量100質量部に対して、0.01~10質量部が好ましく、0.1~5質量部がより好ましい。 Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a water-soluble or oil-soluble radical polymerization initiator is preferable.
As the radical polymerization initiator, a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferable. The polymerization temperature is preferably 30 to 80 ° C.
The addition amount of the polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used for the polymerization.
単量体(b)の割合は、重合に使用する全単量体(100質量%)のうち、0~60質量%が好ましく、0~45質量%がより好ましく、0~30質量%が特に好ましい。
単量体(c)の割合は、重合に使用する全単量体(100質量%)のうち、0~30質量%が好ましく、0~10質量%がより好ましく、0質量%が特に好ましい。 The proportion of the monomer (a) is 40 to 100% by mass from the viewpoint of liquid repellency with respect to the ketone solvent and the ester solvent among the total monomers (100% by mass) used in the polymerization. To 100% by mass is preferable, 70 to 100% by mass is more preferable, and 100% by mass is particularly preferable.
The proportion of the monomer (b) is preferably 0 to 60% by mass, more preferably 0 to 45% by mass, and particularly preferably 0 to 30% by mass, based on the total monomer (100% by mass) used in the polymerization. preferable.
The proportion of the monomer (c) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and particularly preferably 0% by mass, based on the total monomer (100% by mass) used in the polymerization.
含フッ素重合体(B)としては、前記単位(α)を有し、該単位(α)の割合が全構成単位において40質量%未満の含フッ素重合体、または、前記単位(α)を有さず、前記単位(β)を必須とし、必要に応じて前記単位(γ)を有する含フッ素重合体が好ましい。 (Fluoropolymer (B))
The fluorine-containing polymer (B) has the unit (α), and the proportion of the unit (α) is less than 40% by mass in all the structural units, or the unit (α). The fluoropolymer having the unit (β) as an essential component and the unit (γ) as required is preferable.
含フッ素重合体(B)の数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される、ポリメタクリル酸メチル換算の分子量である。 The number average molecular weight (Mn) of the fluoropolymer (B) is preferably from 1,000 to 200,000, more preferably from 5,000 to 50,000. When the number average molecular weight (Mn) of the fluoropolymer (B) is not less than the lower limit, the liquid repellency with respect to the ketone solvent and the ester solvent is improved. If the number average molecular weight (Mn) of the fluoropolymer (B) is not more than the above upper limit value, the film-forming property will be good, and as a result, sufficient liquid repellency for ketone solvents and ester solvents will be obtained.
The number average molecular weight (Mn) of the fluoropolymer (B) is a molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography (GPC).
含フッ素重合体(C)としては、含フッ素環構造を有する単量体を重合して得られる含フッ素重合体、または、少なくとも2つの重合性二重結合を有する含フッ素単量体を環化重合して得られる、主鎖に環構造を有する含フッ素重合体が好ましい。これら含フッ素重合体としては、たとえば、特許第2854223号公報に記載の重合体が挙げられる。 (Fluoropolymer (C))
As the fluorinated polymer (C), a fluorinated polymer obtained by polymerizing a monomer having a fluorinated ring structure, or a fluorinated monomer having at least two polymerizable double bonds is cyclized. A fluoropolymer having a ring structure in the main chain obtained by polymerization is preferred. Examples of these fluoropolymers include the polymers described in Japanese Patent No. 2854223.
含フッ素重合体(C)の割合は、含フッ素重合体(A)の100質量部に対して、0~20質量部が好ましく、0~10質量部がより好ましい。 The proportion of the fluoropolymer (B) is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (A).
The proportion of the fluoropolymer (C) is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (A).
本発明の撥油防水性通気フィルタは、連続多孔質構造を有する基材を、前述した含フッ素重合体(A)を必須成分として含む被覆材料と、媒体とを含む撥油防水剤組成物によって処理し、前記媒体を除去する方法によって製造される。 <Method for producing oil-repellent waterproof breathable filter>
The oil-repellent waterproof breathable filter of the present invention comprises an oil-repellent waterproof agent composition comprising a base material having a continuous porous structure, a coating material containing the above-mentioned fluoropolymer (A) as an essential component, and a medium. Manufactured by a method of processing and removing the media.
HFC、HFEの分子構造は、直鎖状でも分岐鎖状でもよく、直鎖状が好ましい。HFE1分子中に含まれるエーテル性の酸素原子の数は、1個であってもよく、2個以上であってもよい。媒体として使いやすい沸点である点、安定性の点から、1個または2個が好ましく、1個がより好ましい。 The medium of the oil repellent waterproofing agent composition is preferably a fluorine-based medium, more preferably hydrofluorocarbon (hereinafter referred to as “HFC”) or hydrofluoroether (hereinafter referred to as “HFE”). HFC is a compound composed of only carbon atoms, hydrogen atoms, and fluorine atoms, in which part of hydrocarbon hydrogen atoms is replaced by fluorine atoms. The HFC is preferably an HFC that has 4 or more carbon atoms and is liquid at normal temperature and pressure. HFE is a compound containing an etheric oxygen atom between carbon-carbon atoms of HFC. HFE is preferably HFE having 4 or more carbon atoms and liquid at normal temperature and pressure. The normal temperature and normal pressure in this specification means 25 ° C. and 1 atm.
The molecular structure of HFC and HFE may be linear or branched, and is preferably linear. The number of etheric oxygen atoms contained in one HFE molecule may be one or two or more. One or two is preferable and one is more preferable from the viewpoint of a boiling point that is easy to use as a medium and stability.
1,1,1,3,3-ペンタフルオロブタン(CF3CH2CF2CH3)、
1,1,1,2,2,3,4,5,5,5-デカフルオロペンタン(CF3CF2CHFCHFCF3)、
1H-モノデカフルオロペンタン(C5F11H)、
3H-モノデカフルオロペンタン(C5F11H)、
1H-トリデカフルオロヘキサン(C6F13H)、
1H-ペンタデカフルオロヘプタン(C7F15H)、
3H-ペンタデカフルオロヘプタン(C7F15H)、
1H-ヘプタデカフルオロオクタン(C8F17H)、
1H-ノナデカフルオロノナン(C9F19H)、
1H-パーフルオロデカン(C10F21H)、
1,1,1,2,2,3,3,4,4-ノナフルオロヘキサン(C4F9CH2CH3)、
1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン(C6F13CH2CH3)、
1,1,1,2,2,3,3,4,4,5,5,6,6、7,7,8,8-ヘプタデカフルオロデカン(C8F17CH2CH3)等。 Specific examples of HFC include the following compounds.
1,1,1,3,3-pentafluorobutane (CF 3 CH 2 CF 2 CH 3 ),
1,1,1,2,2,3,4,5,5,5-decafluoropentane (CF 3 CF 2 CHFCHFCF 3 ),
1H-monodecafluoropentane (C 5 F 11 H),
3H-monodecafluoropentane (C 5 F 11 H),
1H-tridecafluorohexane (C 6 F 13 H),
1H-pentadecafluoroheptane (C 7 F 15 H),
3H-pentadecafluoroheptane (C 7 F 15 H),
1H-heptadecafluorooctane (C 8 F 17 H),
1H-nonadecafluorononane (C 9 F 19 H),
1H-perfluorodecane (C 10 F 21 H),
1,1,1,2,2,3,3,4,4-nonafluorohexane (C 4 F 9 CH 2 CH 3 ),
1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (C 6 F 13 CH 2 CH 3 ),
1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8- heptadecafluoro decane (C 8 F 17 CH 2 CH 3) or the like.
メチルパーフルオロブチルエーテル(C4F9OCH3)、
エチルパーフルオロブチルエーテル(C4F9OCH2CH3)、
メチルパーフルオロペンチルエーテル(C5F11OCH3)、
エチルパーフルオロペンチルエーテル(C5F11OCH2CH3)、
メチルパーフルオロヘキシルエーテル(C6F13OCH3)、
エチルパーフルオロヘキシルエーテル(C6F13OCH2CH3)、
メチルパーフルオロヘプチルエーテル(C7F15OCH3)、
エチルパーフルオロへプチルエーテル(C7F15OCH2CH3)、
メチルパーフルオロオクチルエーテル(C8F17OCH3)、
エチルパーフルオロオクチルエーテル(C8F17OCH2CH3)、
メチルパーフルオロノニルエール(C9F19OCH3)、
エチルパーフルオロノニルエーテル(C9F19OCH2CH3)、
メチルパーフルオロデシルエーテル(C10F21OCH3)、
エチルパーフルオロデシルエーテル(C10F21OCH2CH3)、
1,1,2,2-テトラフルオロエチル-2,2,2-トリフルオロエチルエーテル(CF3CH2OCF2CF2H)、
1,2,2,2-テトラフルオロエチル-2,2,2-トリフルオロエチルエーテル(CF3CHFOCH2CF3)、
1,1,2,3,3,3-ヘキサフルオロプロピル-2,2,2-トリフルオロエチルエーテル(CF3CH2OCF2CFHCF3)、
1,1,2,2-テトラフルオロエチル-2,2,3,3-テトラフルオロプロピルエーテル(CHF2CF2CH2OCF2CF2H)、
1,1,2,2,3,3-ヘキサフルオロ-1-(1,2,2,2,-テトラフルオロエトキシ)プロピル-パーフルオロプロピルエーテル(C3F7OC3F6OCFHCF3)、
1,1,1,2,3,4,4,5,5,5-デカフルオロ-2-(トリフルオロメチル)-3-(メトキシ)ペンタン(CF3CF(CF3)CF(OCH3)CF2CF3)、
1,1,1,2,3,4,4,5,5,5-デカフルオロ-2-(トリフルオロメチル)-3-(エトキシ)ペンタン(CF3CF(CF3)CF(OC2H5)CF2CF3)、
1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタン(CF2(OCH2CF3)CF2H)、
1,1,2,3,3,3-ヘキサフルオロ-1-(2,2,2-トリフルオロエトキシ)プロパン(CF2(OCH2CF3)CFHCF3)、
1,1,2,2-テトラフルオロ-1-(2,2,3,3-テトラフルオロプロポキシ)エタン(CF2(OCH2CF2CF2H)CF2H)、
1,1,2,3,3,3-ヘキサフルオロ-1-(2,2,3,3-テトラフルオロプロポキシ)プロパン(CF2(OCH2CF2CF2H)CFHCF3)等。 Specific examples of HFE include the following compounds.
Methyl perfluorobutyl ether (C 4 F 9 OCH 3 ),
Ethyl perfluorobutyl ether (C 4 F 9 OCH 2 CH 3 ),
Methyl perfluoropentyl ether (C 5 F 11 OCH 3 ),
Ethyl perfluoropentyl ether (C 5 F 11 OCH 2 CH 3 ),
Methyl perfluorohexyl ether (C 6 F 13 OCH 3 ),
Ethyl perfluorohexyl ether (C 6 F 13 OCH 2 CH 3 ),
Methyl perfluoroheptyl ether (C 7 F 15 OCH 3 ),
Ethyl perfluoro to Petit ether (C 7 F 15 OCH 2 CH 3),
Methyl perfluorooctyl ether (C 8 F 17 OCH 3 ),
Ethyl perfluorooctyl ether (C 8 F 17 OCH 2 CH 3 ),
Methyl perfluorononyl ale (C 9 F 19 OCH 3 ),
Ethyl perfluorononyl ether (C 9 F 19 OCH 2 CH 3 ),
Methyl perfluorodecyl ether (C 10 F 21 OCH 3 ),
Ethyl perfluorodecyl ether (C 10 F 21 OCH 2 CH 3 ),
1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF 3 CH 2 OCF 2 CF 2 H),
1,2,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF 3 CHFOCH 2 CF 3 ),
1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether (CF 3 CH 2 OCF 2 CFHCF 3 ),
1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (CHF 2 CF 2 CH 2 OCF 2 CF 2 H),
1,1,2,2,3,3-hexafluoro-1- (1,2,2,2, -tetrafluoroethoxy) propyl-perfluoropropyl ether (C 3 F 7 OC 3 F 6 OCCFHCF 3 ),
1,1,1,2,3,4,4,5,5,5-decafluoro-2- (trifluoromethyl) -3- (methoxy) pentane (CF 3 CF (CF 3 ) CF (OCH 3 ) CF 2 CF 3 ),
1,1,1,2,3,4,4,5,5,5-decafluoro-2- (trifluoromethyl) -3- (ethoxy) pentane (CF 3 CF (CF 3 ) CF (OC 2 H 5 ) CF 2 CF 3 ),
1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (CF 2 (OCH 2 CF 3 ) CF 2 H),
1,1,2,3,3,3-hexafluoro-1- (2,2,2-trifluoroethoxy) propane (CF 2 (OCH 2 CF 3 ) CFHCF 3 ),
1,1,2,2-tetrafluoro-1- (2,2,3,3-tetrafluoropropoxy) ethane (CF 2 (OCH 2 CF 2 CF 2 H) CF 2 H),
1,1,2,3,3,3-hexafluoro-1- (2,2,3,3-tetrafluoropropoxy) propane (CF 2 (OCH 2 CF 2 CF 2 H) CFHCF 3 ) and the like.
媒体の割合は、含フッ素重合体(A)~(C)の合計量(100質量部)に対して、100~50,000質量部が好ましく、500~10,000質量部がより好ましい。媒体の割合が前記下限値以上であれば、処理効率が向上する。媒体の割合が前記上限値以下であれば、媒体の除去効率が向上する。 A medium may be used individually by 1 type and may use 2 or more types together. As the medium, the medium used for the polymerization of the fluoropolymer (A) or the like may be diluted as necessary.
The ratio of the medium is preferably 100 to 50,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to the total amount (100 parts by mass) of the fluoropolymers (A) to (C). If the ratio of the medium is equal to or higher than the lower limit value, the processing efficiency is improved. If the ratio of the medium is not more than the above upper limit value, the medium removal efficiency is improved.
媒体を除去する方法としては、たとえば、風乾、または熱処理により媒体を蒸発させる方法が挙げられる。媒体を除去する際の温度は、50~200℃が好ましく、撥油性能が向上する点から、100~150℃がより好ましい。 Examples of the method for treating the substrate with the oil repellent waterproofing agent composition include dip coating and spray coating.
Examples of the method for removing the medium include a method of evaporating the medium by air drying or heat treatment. The temperature for removing the medium is preferably 50 to 200 ° C., and more preferably 100 to 150 ° C. from the viewpoint of improving oil repellency.
[数平均分子量(Mn)]
ゲルパーミエーションクロマトグラフィー(GPC:東ソーHLC-8220、カラム:ポリマーラボラトリーPLgel MIXED-C(5μm)、溶媒:アサヒクリンAK-225(旭硝子社製、3,3-ジクロロ-1,1,1,2,2-ペンタフルオロプロパンと1,3-ジクロロ-1,1,2,2,3-ペンタフルオロプロパンとの混合物、フッ素重量分率:46.8質量%)/ヘキサフルオロイソプロパノール=99/1(体積比)の混合溶媒、カラム温度:40℃、ポリメタクリル酸メチル換算)により、含フッ素重合体の数平均分子量(Mn)を測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. Hereinafter, “part” means “part by mass”, and “MEK” means “methyl ethyl ketone”. Examples 8, 9, 13 to 15, 17, and 18 are examples, examples 10 to 12 and 16 are comparative examples, and examples 19 and 20 are reference examples.
[Number average molecular weight (Mn)]
Gel permeation chromatography (GPC: Tosoh HLC-8220, Column: Polymer Laboratory PLgel MIXED-C (5 μm), Solvent: Asahiklin AK-225 (Asahi Glass Co., Ltd., 3,3-dichloro-1,1,1,2) , 2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane, fluorine weight fraction: 46.8% by mass) / hexafluoroisopropanol = 99/1 ( The volume average molecular weight (Mn) of the fluorine-containing polymer was measured using a mixed solvent (volume ratio), column temperature: 40 ° C., polymethyl methacrylate equivalent).
含フッ素重合体のフッ素重量分率は、燃焼・ピロヒドロリシス法(燃焼条件はM. Noshiro, T. Yarita, Japan analyst 1977, 26, 721-723に準ずる。 [Fluorine weight fraction]
The fluorine weight fraction of the fluorinated polymer is in accordance with the combustion and pyrohydrolysis method (combustion conditions are M. Noshiro, T. Yarita, Japan analyst 1977, 26, 721-723).
[例1]
単量体(a)であるα-クロロペルフルオロアルキルアクリレート(CH2=CClCOOCH2CH2C6F13)(以下、「α-ClC6FA」と記す。)の5g、アサヒクリンAK-225(旭硝子社製)の45g、および重合開始剤としてアゾビスイソブチロニトリルの0.05gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、65℃で15時間重合を行った。その結果、RF基を有する含フッ素重合体A1を10質量%含む溶液を得た。前記溶液を、ヘプタンの500gを入れた1Lのガラス製フラスコに撹拌しながら投入し、その後、上澄み液をデカンテーションにより取り除くことで、含フッ素重合体A1を含む固形物を得た。該固形物を乾燥することで含フッ素重合体A1を4.5g得た。
含フッ素重合体A1の数平均分子量は17,000であった。また、含フッ素重合体A1のフッ素重量分率を測定したところ54.5質量%(理論値54.6質量%)であった。 <Production example of fluoropolymer>
[Example 1]
5 g of monomer (a) α-chloroperfluoroalkyl acrylate (CH 2 ═CClCOOCH 2 CH 2 C 6 F 13 ) (hereinafter referred to as “α-ClC6FA”), Asahi Klin AK-225 (Asahi Glass Co., Ltd.) ) And 0.05 g of azobisisobutyronitrile as a polymerization initiator were placed in a pressure-resistant glass ampoule (100 mL). After the system was replaced with nitrogen three times, polymerization was carried out at 65 ° C. for 15 hours. As a result, to obtain a solution containing a fluorine-containing polymer A1 having a R F group 10 wt%. The solution was put into a 1 L glass flask containing 500 g of heptane with stirring, and then the supernatant was removed by decantation to obtain a solid containing the fluoropolymer A1. The solid was dried to obtain 4.5 g of a fluoropolymer A1.
The number average molecular weight of the fluoropolymer A1 was 17,000. Moreover, it was 54.5 mass% (theoretical value 54.6 mass%) when the fluorine weight fraction of fluoropolymer A1 was measured.
単量体(b)であるペルフルオロアルキルメタクリレート(CH2=CCH3COOCH2CH2C6F13)(以下、「C6FMA」と記す。)の20g、アサヒクリンAK-225の46.7g、および重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)の0.11gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、50℃で48時間重合を行った。その結果、RF基を有する含フッ素重合体B1を10質量%含む溶液を得た。前記溶液を、メタノールの1,000gを入れた2Lのガラス製フラスコに撹拌しながら投入した。その後、沈殿物を含む混合物を濾過し、含フッ素重合体B1を含む固形物を得た。該固形物を乾燥することで含フッ素重合体B1を19g得た。
含フッ素重合体B1の数平均分子量は33,000であった。また、含フッ素重合体B1のフッ素重量分率を測定したところ57.7質量%(理論値57.2質量%)であった。 [Example 2]
20 g of perfluoroalkyl methacrylate (CH 2 ═CCH 3 COOCH 2 CH 2 C 6 F 13 ) (hereinafter referred to as “C6FMA”) as the monomer (b), 46.7 g of Asahiclin AK-225, and As a polymerization initiator, 0.11 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, to obtain a solution containing a fluorine-containing polymer B1 having a R F group 10 wt%. The solution was charged into a 2 L glass flask containing 1,000 g of methanol with stirring. Thereafter, the mixture containing the precipitate was filtered to obtain a solid containing the fluoropolymer B1. 19g of fluoropolymer B1 was obtained by drying this solid substance.
The number average molecular weight of the fluoropolymer B1 was 33,000. Further, the fluorine weight fraction of the fluoropolymer B1 was measured and found to be 57.7% by mass (theoretical value: 57.2% by mass).
単量体(a)であるα-ClC6FAの8g、アサヒクリンAC-6000(旭硝子社製、C6F13C2H5、フッ素重量分率:71.0質量%)の72g、および重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)の0.24gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、50℃で48時間重合を行った。その結果、RF基を有する含フッ素重合体A2を10質量%含む溶液を80g得た。含フッ素重合体A2の数平均分子量は17,000であった。 [Example 3]
8 g of α-ClC6FA as the monomer (a), 72 g of Asahiklin AC-6000 (Asahi Glass Co., Ltd., C 6 F 13 C 2 H 5 , fluorine weight fraction: 71.0 mass%), and polymerization start As an agent, 0.24 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A2 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A2 was 17,000.
単量体(a)であるα-ClC6FAの7.2g、単量体(b)であるC6FMAの0.8g、アサヒクリンAC-6000の72g、および重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)の0.24gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、50℃で48時間重合を行った。その結果、RF基を有する含フッ素重合体A3を10質量%含む溶液を80g得た。含フッ素重合体A3の数平均分子量は17,000であった。 [Example 4]
7.2 g of monomer (a) α-ClC6FA, 0.8 g of C6FMA monomer (b), 72 g of Asahiklin AC-6000, and 2,2′-azobis ( 0.24 g of 2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A3 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A3 was 17,000.
単量体(a)であるα-ClC6FAの4.8g、単量体(b)であるC6FMAの3.2g、アサヒクリンAC-6000の72g、および重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)の0.24gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、50℃で48時間重合を行った。その結果、RF基を有する含フッ素重合体A4を10質量%含む溶液を80g得た。含フッ素重合体A4の数平均分子量は15,000であった。 [Example 5]
4.8 g of monomer (a) α-ClC6FA, 3.2 g of monomer (b) C6FMA, 72 g of Asahiklin AC-6000, and 2,2′-azobis ( 0.24 g of 2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. As a result, a solution containing a fluorine-containing polymer A4 having a R F group 10 wt% were obtained 80 g. The number average molecular weight of the fluoropolymer A4 was 15,000.
単量体(a)であるα-ClC6FAの2.4g、単量体(b)であるC6FMAの5.6g、アサヒクリンAC-6000の72g、および重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)の0.24gを耐圧ガラスアンプル(100mL)に入れた。系内を3回窒素で置換した後、50℃で48時間重合を行った。その結果RF基を有する含フッ素重合体B2を10質量%含む溶液を80g得た。含フッ素重合体B2の数平均分子量は12,000であった。 [Example 6]
Monomer (a) α-ClC6FA 2.4 g, Monomer (b) C6FMA 5.6 g, Asahiclin AC-6000 72 g, and 2,2′-azobis ( 0.24 g of 2,4-dimethylvaleronitrile) was placed in a pressure-resistant glass ampoule (100 mL). After substituting the inside of the system with nitrogen three times, polymerization was carried out at 50 ° C. for 48 hours. The solution resulting comprising 10 wt% of a fluorine-containing polymer B2 having an R F group to give 80 g. The number average molecular weight of the fluoropolymer B2 was 12,000.
サイトップCTX-109AE(旭硝子社製、(C6F10O)n、フッ素重量分率:68.3質量%)をPTFE製の容器に入れ、200℃で1時間乾燥させることにより、主鎖に含フッ素脂肪族環構造を有する含フッ素重合体C1を得た。
例1~6の単量体組成および含フッ素重合体の数平均分子量(Mn)を表1に示す。 [Example 7]
Cytop CTX-109AE (Asahi Glass Co., Ltd., (C 6 F 10 O) n , fluorine weight fraction: 68.3 mass%) is put in a PTFE container and dried at 200 ° C. for 1 hour to form a main chain. Thus, a fluorinated polymer C1 having a fluorinated aliphatic ring structure was obtained.
Table 1 shows the monomer compositions of Examples 1 to 6 and the number average molecular weights (Mn) of the fluoropolymers.
[例8]
例1で得た含フッ素重合体A1の2.0部を、媒体であるアサヒクリンAC-6000(HFC)の100部に溶解して撥油防水剤組成物を調製した。その後、ディップコート(引き上げ速度:5mm/秒)により、基材である延伸多孔質PTFEシート(孔径1μm、厚さ300μm、空孔率60%(共に公称値))を前記撥油防水剤組成物によって処理し、150℃で10分間乾燥して媒体を除去して試料1を得た。得られた試料1について、濡れ性試験を行った。 <Evaluation of wettability>
[Example 8]
An oil repellent waterproofing agent composition was prepared by dissolving 2.0 parts of the fluoropolymer A1 obtained in Example 1 in 100 parts of the medium Asahiclin AC-6000 (HFC). Thereafter, the stretched porous PTFE sheet (pore diameter: 1 μm, thickness: 300 μm, porosity: 60% (both nominal values)) as a base material is applied to the oil repellent waterproofing composition by dip coating (pickup speed: 5 mm / second). Sample 1 was obtained by removing the medium by drying at 150 ° C. for 10 minutes. About the obtained sample 1, the wettability test was done.
例1で得た含フッ素重合体A1の1.98部および例7で得た含フッ素重合体C1の0.02部を、媒体であるアサヒクリンAC-6000の100部に溶解して撥油防水剤組成物を調製した以外は、例8と同様にして試料2を作製した。得られた試料2について、濡れ性試験を行った。 [Example 9]
1.98 parts of the fluorinated polymer A1 obtained in Example 1 and 0.02 part of the fluorinated polymer C1 obtained in Example 7 were dissolved in 100 parts of the medium ASAHIKLIN AC-6000 to make the oil repellent. Sample 2 was prepared in the same manner as in Example 8 except that the waterproofing agent composition was prepared. About the obtained sample 2, the wettability test was done.
例2で得た含フッ素重合体B1の2.0部を、媒体であるアサヒクリンAC-6000の100部に溶解して撥油防水剤組成物を調製した以外は、例8と同様にして試料3を作製した。得られた試料3について、濡れ性試験を行った。 [Example 10]
Except for preparing an oil repellent waterproofing composition by dissolving 2.0 parts of the fluoropolymer B1 obtained in Example 2 in 100 parts of the medium Asahiclin AC-6000, the same procedure as in Example 8 was performed. Sample 3 was prepared. The obtained sample 3 was subjected to a wettability test.
例2で得た含フッ素重合体B1の1.98部および例7で得た含フッ素重合体C1の0.02部を、媒体であるアサヒクリンAC-6000の100部に溶解して撥油防水剤組成物を調製した以外は、例8と同様にして試料4を作製した。得られた試料4について、濡れ性試験を行った。 [Example 11]
1.98 parts of the fluoropolymer B1 obtained in Example 2 and 0.02 part of the fluoropolymer C1 obtained in Example 7 were dissolved in 100 parts of the medium Asahiclin AC-6000 to make the oil repellent. Sample 4 was prepared in the same manner as in Example 8 except that the waterproofing agent composition was prepared. The obtained sample 4 was subjected to a wettability test.
基材である延伸多孔質PTFEシートを未処理のまま試料5とし、濡れ性試験を行った。 [Example 12]
The stretched porous PTFE sheet as the base material was used as a sample 5 untreated, and a wettability test was performed.
水平に置いた試料の表面に、ピペットを使用して試験用液体(n-ヘキサン、n-デカン、アセトン、MEK、エタノール)を液滴状(1滴が約10~50μL)に静かに垂らし、目視により濡れの状態、浸透の有無を観察した。一般に濡れた多孔質試料は半透明から透明に変化する。試験は同一条件で作成した2枚の試料に対して、それぞれの試料表面に試験用液体を3ヵ所ずつ合計6ヵ所滴下し、滴下30秒後の濡れ性を以下の基準で評価した。「○」:6ヶ所すべてにおいて濡れまたは浸透がなかった。「△」:1ヵ所以上で濡れまたは浸透があるものの、試験用液体が液滴の形状を保っていた。「×」:1ヵ所以上で試験用液体が液滴形状を保てない程度の濡れまたは浸透があった。
例8~12における濡れ性試験の結果を表2に示す。 [Wettability test]
Using a pipette, gently drop the test liquid (n-hexane, n-decane, acetone, MEK, ethanol) into droplets (about 10-50 μL each drop) on the surface of the sample placed horizontally. The wet state and the presence or absence of penetration were observed visually. In general, a wet porous sample changes from translucent to transparent. The test was performed on two samples prepared under the same conditions by dropping three test liquids on each sample surface in a total of six places, and the wettability after 30 seconds of dropping was evaluated according to the following criteria. “◯”: There was no wetting or penetration at all six locations. “Δ”: Although there was wetting or penetration at one or more locations, the test liquid maintained the shape of the droplets. “X”: There was wetness or permeation to such an extent that the test liquid could not maintain the droplet shape at one or more locations.
The results of the wettability test in Examples 8 to 12 are shown in Table 2.
例3で得た含フッ素重合体A2の10質量%溶液の20部に、さらにアサヒクリンAC-6000の80部を加えて希釈して撥油防水剤組成物を調製した以外は、例8と同様にして試料6を得た。得られた試料6について、濡れ性試験を行った。 [Example 13]
Except that an oil repellent waterproofing agent composition was prepared by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A2 obtained in Example 3 to prepare an oil repellent waterproofing composition. Sample 6 was obtained in the same manner. The obtained sample 6 was subjected to a wettability test.
例4で得た含フッ素重合体A3の10質量%溶液の20部に、さらにアサヒクリンAC-6000の80部を加えて希釈して撥油防水剤組成物を調製した以外は、例8と同様にして試料7を得た。得られた試料7について、濡れ性試験を行った。 [Example 14]
Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A3 obtained in Example 4, and preparing an oil repellent waterproofing composition. Sample 7 was obtained in the same manner. About the obtained sample 7, the wettability test was done.
例5で得た含フッ素重合体A4の10質量%溶液の20部に、さらにアサヒクリンAC-6000の80部を加えて希釈して撥油防水剤組成物を調製した以外は、例8と同様にして試料8を得た。得られた試料8について、濡れ性試験を行った。 [Example 15]
Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of a 10% by mass solution of the fluoropolymer A4 obtained in Example 5, and preparing an oil repellent waterproofing composition. Sample 8 was obtained in the same manner. The obtained sample 8 was subjected to a wettability test.
例6で得た含フッ素重合体B2の10質量%溶液の20部に、さらにアサヒクリンAC-6000の80部を加えて希釈して撥油防水剤組成物を調製した以外は、例8と同様にして試料9を得た。得られた試料9について、濡れ性試験を行った。
例10および例13~16における濡れ性試験の結果を表3に示す。 [Example 16]
Except for preparing an oil repellent waterproofing composition by adding 80 parts of Asahiclin AC-6000 to 20 parts of the 10% by mass solution of the fluoropolymer B2 obtained in Example 6, and preparing an oil repellent waterproofing agent composition. Sample 9 was obtained in the same manner. About the obtained sample 9, the wettability test was done.
The results of the wettability test in Example 10 and Examples 13 to 16 are shown in Table 3.
例3で得た含フッ素重合体A2の10質量%溶液の10gを、メタノールの200gを入れた500mLのガラス製フラスコに撹拌しながら投入した後、上澄み液をデカンテーションにより取り除くことで、含フッ素重合体A2を含む固形物を得た。その後、該固形物を乾燥することでペルフルオロアルキル基を有する含フッ素重合体A2(数平均分子量17,000)を0.9g得た。
得られた含フッ素重合体A2の2.0部をHFE-7300(住友スリーエム社製、C6F13OCH3、フッ素重量分率:70.6質量%)の100部に溶解して撥油防水剤組成物を調製した。得られた撥油防水剤組成物を使用して、例8と同様にして試料10を得た。得られた試料10について、濡れ性試験を行った。 [Example 17]
10 g of the 10% by mass solution of the fluoropolymer A2 obtained in Example 3 was added to a 500 mL glass flask containing 200 g of methanol while stirring, and then the supernatant was removed by decantation. A solid containing polymer A2 was obtained. Then, 0.9g of fluoropolymer A2 (number average molecular weight 17,000) which has a perfluoroalkyl group was obtained by drying this solid substance.
2.0 parts of the obtained fluorinated polymer A2 was dissolved in 100 parts of HFE-7300 (manufactured by Sumitomo 3M, C 6 F 13 OCH 3 , fluorine weight fraction: 70.6 mass%) to make it oil repellent. A waterproofing agent composition was prepared. Sample 10 was obtained in the same manner as Example 8 using the obtained oil repellent waterproofing composition. About the obtained sample 10, the wettability test was done.
例3で得た含フッ素重合体A2の10質量%溶液の代わりに、例4で得た含フッ素重合体A3の10質量%溶液を使用した以外は、例17と同様にして撥油防水剤組成物を調製した。その後、得られた撥油防水剤組成物を使用して、例8と同様にして試料11を得た。得られた試料11について、濡れ性試験を行った。
例17および例18における濡れ性試験の結果を表4に示す。 [Example 18]
Oil repellent waterproofing agent in the same manner as in Example 17 except that the 10% by mass solution of the fluoropolymer A3 obtained in Example 4 was used instead of the 10% by mass solution of the fluoropolymer A2 obtained in Example 3. A composition was prepared. Then, the sample 11 was obtained like Example 8 using the obtained oil-repellent waterproofing agent composition. About the obtained sample 11, the wettability test was done.
Table 4 shows the results of the wettability test in Examples 17 and 18.
[例19]
例1で得た含フッ素重合体A1の10質量%溶液の20部に、さらにアサヒクリンAC-6000の80部を加えて希釈して撥油防水剤組成物を調製した。その後、ディップコート(引き上げ速度:5mm/秒)により、ガラス基板を前記撥油防水剤組成物によって処理し、150℃で1時間乾燥して試料12を得た。得られた試料12について、接触角測定(1秒後、21秒後)を行った。 <Reference example>
[Example 19]
An oil repellent waterproofing composition was prepared by adding 80 parts of Asahiclin AC-6000 to 20 parts of the 10% by mass solution of the fluoropolymer A1 obtained in Example 1 and diluting. Thereafter, the glass substrate was treated with the oil repellent waterproofing agent composition by dip coating (pickup speed: 5 mm / second), and dried at 150 ° C. for 1 hour to obtain Sample 12. The obtained sample 12 was subjected to contact angle measurement (after 1 second and after 21 seconds).
例1で得た含フッ素重合体A1の10質量%溶液の代わりに、例2で得た含フッ素重合体B1の10質量%溶液を使用した以外は、例19と同様にして試料13を得た。得られた試料13について、接触角測定を行った。 [Example 20]
A sample 13 was obtained in the same manner as in Example 19 except that the 10% by mass solution of the fluoropolymer B1 obtained in Example 2 was used instead of the 10% by mass solution of the fluoropolymer A1 obtained in Example 1. It was. The obtained sample 13 was subjected to contact angle measurement.
下記装置および条件によって試験用液体(酢酸エチル、酢酸ブチル、MEK、水、n-デカン)の接触角を測定した。
手法:液滴法
使用装置:自動接触角計 DM-500(協和界面科学株式会社)
液滴量:1.8-2.2μL
解析法:θ/2法
例19および例20における接触角測定の結果を表5に示す。 [Contact angle]
The contact angle of the test liquid (ethyl acetate, butyl acetate, MEK, water, n-decane) was measured according to the following apparatus and conditions.
Method: Droplet method Equipment: Automatic contact angle meter DM-500 (Kyowa Interface Science Co., Ltd.)
Drop volume: 1.8-2.2 μL
Analysis method: θ / 2 method Table 5 shows the results of contact angle measurement in Examples 19 and 20.
なお、2010年12月22日に出願された日本特許出願2010-286566号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The oil-repellent waterproof breathable filter of the present invention is useful as a filter used for an exhaust gas sensor of an automobile, an ink cartridge of an inkjet printer, and the like.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2010-286666 filed on Dec. 22, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.
Claims (6)
- 連続多孔質構造を有する基材が、ペルフルオロアルキル基を有する含フッ素重合体を含む被覆材料によって被覆された撥油防水性通気フィルタであって、
前記含フッ素重合体が、下記単量体(a)に基づく構成単位を有し、該構成単位の割合が全構成単位において40~100質量%であることを特徴とする撥油防水性通気フィルタ。
単量体(a):α位が塩素原子であり、炭素数1~6のペルフルオロアルキル基を有するアクリレート。 The base material having a continuous porous structure is an oil-repellent waterproof breathable filter coated with a coating material containing a fluoropolymer having a perfluoroalkyl group,
The fluorinated polymer has structural units based on the following monomer (a), and the proportion of the structural units is 40 to 100% by mass in all the structural units. .
Monomer (a): an acrylate having a chlorine atom at the α-position and having a C 1-6 perfluoroalkyl group. - 前記単量体(a)が、α位が塩素原子であり、炭素数6のペルフルオロアルキル基を有するアクリレートである請求項1に記載の撥油防水性通気フィルタ。 The oil-repellent waterproof breathable filter according to claim 1, wherein the monomer (a) is an acrylate having a chlorine atom at the α-position and having a C 6 perfluoroalkyl group.
- 前記基材がポリテトラフルオロエチレンからなる請求項1または2に記載の撥油防水性通気フィルタ。 The oil-repellent waterproof breathable filter according to claim 1 or 2, wherein the substrate is made of polytetrafluoroethylene.
- 連続多孔質構造を有する基材を、ペルフルオロアルキル基を有する含フッ素重合体を含む被覆材料と媒体とを含む撥油防水剤組成物によって処理し、前記媒体を除去する撥油防水性通気フィルタの製造方法であって、
前記含フッ素重合体が、下記単量体(a)に基づく構成単位を有し、該構成単位の割合が全構成単位において40~100質量%であることを特徴とする撥油防水性通気フィルタの製造方法。
単量体(a):α位が塩素原子であり、炭素数1~6のペルフルオロアルキル基を有するアクリレート。 An oil-repellent waterproof breathable filter for treating a substrate having a continuous porous structure with an oil-repellent waterproofing composition comprising a coating material containing a fluoropolymer having a perfluoroalkyl group and a medium, and removing the medium A manufacturing method comprising:
The fluorinated polymer has structural units based on the following monomer (a), and the proportion of the structural units is 40 to 100% by mass in all the structural units. Manufacturing method.
Monomer (a): an acrylate having a chlorine atom at the α-position and having a C 1-6 perfluoroalkyl group. - 前記基材がポリテトラフルオロエチレンからなる請求項4に記載の撥油防水性通気フィルタの製造方法。 The method for producing an oil-repellent waterproof breathable filter according to claim 4, wherein the substrate is made of polytetrafluoroethylene.
- 前記媒体が、ハイドロフルオロカーボンおよびハイドロフルオロエーテルからなる群から選ばれる1種以上である請求項4または5に記載の撥油防水性通気フィルタの製造方法。 The method for producing an oil-repellent waterproof breathable filter according to claim 4 or 5, wherein the medium is at least one selected from the group consisting of hydrofluorocarbons and hydrofluoroethers.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137012444A KR20140020832A (en) | 2010-12-22 | 2011-12-19 | Oil-repellent waterproof air-permeable filter and method for producing same |
EP11851057.7A EP2656894A1 (en) | 2010-12-22 | 2011-12-19 | Oil-repellent waterproof air-permeable filter and method for producing same |
US13/924,924 US20130283744A1 (en) | 2010-12-22 | 2013-06-24 | Oil repellent waterproof air-permeable filter and its production process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010286566A JP2012130885A (en) | 2010-12-22 | 2010-12-22 | Oil-repellent waterproof air-permeable filter and method for producing the same |
JP2010-286566 | 2010-12-22 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/924,924 Continuation US20130283744A1 (en) | 2010-12-22 | 2013-06-24 | Oil repellent waterproof air-permeable filter and its production process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012086606A1 true WO2012086606A1 (en) | 2012-06-28 |
Family
ID=46313875
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/079415 WO2012086606A1 (en) | 2010-12-22 | 2011-12-19 | Oil-repellent waterproof air-permeable filter and method for producing same |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130283744A1 (en) |
EP (1) | EP2656894A1 (en) |
JP (1) | JP2012130885A (en) |
KR (1) | KR20140020832A (en) |
TW (1) | TW201236741A (en) |
WO (1) | WO2012086606A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013150781A1 (en) * | 2012-04-06 | 2013-10-10 | 日東電工株式会社 | Breathable sheet imparted with oil repellent properties |
WO2013150780A1 (en) * | 2012-04-06 | 2013-10-10 | 日東電工株式会社 | Breathable film imparted with oil repellent properties |
US9508971B2 (en) | 2011-02-28 | 2016-11-29 | Nitto Denko Corporation | Gas-permeable filter provided with oil repellency |
CN115819912A (en) * | 2022-10-12 | 2023-03-21 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretched film and preparation method thereof |
WO2023189277A1 (en) * | 2022-03-30 | 2023-10-05 | Ntn株式会社 | Bearing device |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014208422A1 (en) * | 2013-06-28 | 2014-12-31 | ダイキン工業株式会社 | Surface treatment agent and fluorine-containing polymer |
CN106165040B (en) * | 2014-04-04 | 2019-01-22 | 东洋纺株式会社 | electret |
CN108136298B (en) * | 2015-10-02 | 2020-08-28 | 东洋纺株式会社 | Electret and electret filter material |
CN108017745B (en) * | 2016-11-01 | 2021-12-10 | 大金工业株式会社 | Fluorine-containing polymer and surface treatment agent composition |
JP6901897B2 (en) * | 2017-04-04 | 2021-07-14 | Agcセイミケミカル株式会社 | Mixed solvent and surface treatment agent |
KR102281760B1 (en) | 2018-07-12 | 2021-07-23 | 주식회사 엘지화학 | Porous fluorine resin composite membrane and method for prepararing the same |
JP7262324B2 (en) * | 2019-06-28 | 2023-04-21 | 富士フイルム株式会社 | Molded article, method for producing molded article, composition, and method for producing composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07126428A (en) * | 1993-09-08 | 1995-05-16 | Japan Gore Tex Inc | Oil repellent, waterproof and air-permeable filter |
JPH08206422A (en) | 1995-02-09 | 1996-08-13 | Nitto Denko Corp | Waterproof-dustproof air-permeable material |
JPH09103662A (en) * | 1995-10-10 | 1997-04-22 | Sumitomo Electric Ind Ltd | Oil-repelling and water-repelling filter |
WO2005047416A1 (en) * | 2003-11-13 | 2005-05-26 | Daikin Industries, Ltd. | Aqueous liquid dispersion of water and oil repellent agent containing nonionic surfactant |
WO2008041750A1 (en) * | 2006-10-05 | 2008-04-10 | Asahi Glass Company, Limited | Fluorinated polymer, method of producing the same and water- and oil-repellent composition |
JP2009242679A (en) * | 2008-03-31 | 2009-10-22 | Daikin Ind Ltd | Highly purified fluorine-containing monomer composition and surface treating agent including polymer of the composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10244110A (en) * | 1997-03-06 | 1998-09-14 | Nitto Denko Corp | Bag filter formed by laminating tetrafluoroethylene on cloth and its production |
JP2000342919A (en) * | 1999-06-09 | 2000-12-12 | Nitto Denko Corp | Ventilation filter and ventilation member using the same |
JP2008136908A (en) * | 2006-11-30 | 2008-06-19 | Nitto Denko Corp | Water-repellent air-permeable material |
-
2010
- 2010-12-22 JP JP2010286566A patent/JP2012130885A/en active Pending
-
2011
- 2011-12-19 EP EP11851057.7A patent/EP2656894A1/en not_active Withdrawn
- 2011-12-19 WO PCT/JP2011/079415 patent/WO2012086606A1/en active Application Filing
- 2011-12-19 KR KR1020137012444A patent/KR20140020832A/en not_active Application Discontinuation
- 2011-12-21 TW TW100147713A patent/TW201236741A/en unknown
-
2013
- 2013-06-24 US US13/924,924 patent/US20130283744A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07126428A (en) * | 1993-09-08 | 1995-05-16 | Japan Gore Tex Inc | Oil repellent, waterproof and air-permeable filter |
JP2854223B2 (en) | 1993-09-08 | 1999-02-03 | ジャパンゴアテックス株式会社 | Oil repellent waterproof ventilation filter |
JPH08206422A (en) | 1995-02-09 | 1996-08-13 | Nitto Denko Corp | Waterproof-dustproof air-permeable material |
JPH09103662A (en) * | 1995-10-10 | 1997-04-22 | Sumitomo Electric Ind Ltd | Oil-repelling and water-repelling filter |
WO2005047416A1 (en) * | 2003-11-13 | 2005-05-26 | Daikin Industries, Ltd. | Aqueous liquid dispersion of water and oil repellent agent containing nonionic surfactant |
WO2008041750A1 (en) * | 2006-10-05 | 2008-04-10 | Asahi Glass Company, Limited | Fluorinated polymer, method of producing the same and water- and oil-repellent composition |
JP2009242679A (en) * | 2008-03-31 | 2009-10-22 | Daikin Ind Ltd | Highly purified fluorine-containing monomer composition and surface treating agent including polymer of the composition |
Non-Patent Citations (1)
Title |
---|
M. NOSHIRO; T. YARITA, JAPAN ANALYST, vol. 26, 1977, pages 721 - 723 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9508971B2 (en) | 2011-02-28 | 2016-11-29 | Nitto Denko Corporation | Gas-permeable filter provided with oil repellency |
WO2013150781A1 (en) * | 2012-04-06 | 2013-10-10 | 日東電工株式会社 | Breathable sheet imparted with oil repellent properties |
WO2013150780A1 (en) * | 2012-04-06 | 2013-10-10 | 日東電工株式会社 | Breathable film imparted with oil repellent properties |
JP2013216747A (en) * | 2012-04-06 | 2013-10-24 | Nitto Denko Corp | Breathable film imparted with oil repellency |
US9168472B2 (en) | 2012-04-06 | 2015-10-27 | Nitto Denko Corporation | Air-permeable film imparted with oil repellency |
US9255209B2 (en) | 2012-04-06 | 2016-02-09 | Nitto Denko Corporation | Air-permeable sheet imparted with oil repellency |
WO2023189277A1 (en) * | 2022-03-30 | 2023-10-05 | Ntn株式会社 | Bearing device |
CN115819912A (en) * | 2022-10-12 | 2023-03-21 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretched film and preparation method thereof |
CN115819912B (en) * | 2022-10-12 | 2023-07-14 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretched film and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US20130283744A1 (en) | 2013-10-31 |
TW201236741A (en) | 2012-09-16 |
JP2012130885A (en) | 2012-07-12 |
EP2656894A1 (en) | 2013-10-30 |
KR20140020832A (en) | 2014-02-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012086606A1 (en) | Oil-repellent waterproof air-permeable filter and method for producing same | |
CN101730578B (en) | Composite material | |
JP6616395B2 (en) | Spray coating system components and methods including a repellent surface | |
KR101233446B1 (en) | Aqueous delivery system for low surface energy structures | |
JP5866228B2 (en) | Breathable filter with oil repellency | |
WO2003086595A1 (en) | Hydrophobic membrane materials for filter venting applications | |
JP6246481B2 (en) | Breathable filter with adhesive layer with oil repellency | |
US20200139305A1 (en) | Filter For Separating Hydrophilic And Hydrophobic Fluids And Method For The Production Thereof | |
CN104602797B (en) | Impart the breathable filter of oil repellent | |
EP1985355B1 (en) | Composite material | |
JP7180830B2 (en) | Porous fluororesin composite membrane and method for producing the same | |
JP6548173B2 (en) | Fluoropolymer and Membrane Containing Fluoropolymer (III) | |
WO2022113604A1 (en) | Liquid separation membrane and method for producing same | |
US20230311070A1 (en) | Surface-treated porous materials having filtration properties and methods of preparing them | |
TW202311298A (en) | Oleophobic fluoropolymers and filter materials prepared therefrom | |
WO2014151396A1 (en) | Aqueous delivery system for low surface energy structures |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11851057 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137012444 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2011851057 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011851057 Country of ref document: EP |